CS201520B2 - Fungicide means - Google Patents

Abstract

Triazolylglycol ethers of the formula <IMAGE> in which R<1> denotes an alkyl radical having up to 5 C atoms, an alkenyl radical having 3 to 5 C atoms, an alkynyl radical having 3 to 5 C atoms or a benzyl radical which is optionally substituted by halogen, alkoxy or trifluoromethyl, R<2> denotes a halogen atom and n denotes 1 or 2 and their salts and metal complex compounds having good fungicidal activity, fungicides which contain these compounds as active substances, and methods for the control of fungi using these compounds.

Description

The invention relates to a fungicidal composition comprising, as an active ingredient, at least one of the valuable novel substituted triazolylglycol olethers or a salt thereof or a complex compound with a metal. The novel compounds have fungicidal properties. The invention also relates to a process for the preparation of these novel substances.

It is already known to use substituted imidazolyl ethers as fungicides to combat phytopathogenic fungi (cf. DOS 2,063,857).

It has now been found that the triazolyl glycol ethers of formula 1

(

in which

R ¹ represents an alkyl group having up to 5 carbon atoms, alkenyl having 3 or analytically 5 carbon atoms, alk toll group having 3-5 carbon atoms or benzyl skupenu, which is optionally substituted by halogen or, triřluo-rmethylcvou group

R ² is halogen and n is 1 or 2 and a ^CH salts and their complex compounds with metals have very good fungicidal activity with excellent toleration by plants. Salts are, for example, hydrochloride, hydrobromiide, sulphate, oxalate, nitrate or dodecylbenzenesulfonates.

Complex compounds and metals have the general formula II

in which

R 1, R ² 'and n are as defined above, Me means a metal cation, for example a cation of copper, zinc or tin, and

Y is an anion of an inorganic acid, e.g. hydrochloric acid, hydrobromic acid, sulfuric acid or nitric acid, and m is an integer from 1 to 4.

According to the invention, the novel triazolylglycol olethers of formula (I) are prepared by the formation of a triazolyl derivative of formula (III).

(III) in which:

R2 and n are as defined above, in the reaction

a) with a halogenated derivative of the general formula

IV

Hal-R ¹ (IV) wherein

R 1 is as defined above, and

Hal represents halogen, in particular chlorine, bromine or iodine, or both with a sulfonic acid ester of the formula (V),

O

II

RM-0-R1

O (V) in which

R 1 is as defined above, and

R ³ is -O-R 1, phenyl, p-tolyl or -O. p-bromophenyl, in the presence of a solvent and optionally in the presence of a basic catalyst and optionally a Crown ether as further catalyst. ......

Furthermore, the triazolyl glycothers of the formula I obtained by the process according to the invention can be converted by reaction with acids into salts, or the corresponding metal complexes can be obtained by reaction with metal salts.

When 1- [4-chlorophenoxy] -1-C1,2,4-triazol-1-yl] -3,3-dimethylbutan-2-ol was used as starting material. and benzyl bromide, the reaction sequence can be illustrated by the following reaction scheme [process a)]:

Cl

When 1- (4-bromophenoxy) -1- (1,2,4-thi; 2z-11-yl) -3,3-dimethyrbutan-4-ol and dimethyl sulfate are used as starting materials, the reaction scheme may be illustrated by the following reaction scheme. · [Procedure (b)]:

OH their ^ c-ch-

> ^{ICH 3}} 3 ^C

The triazolyl derivatives which are used as starting materials are generally defined by Formula III. (Cf. DOS 2 324 010). ~

The halogen derivatives required for the preparation of the active compounds according to the invention according to process variant a '' are generally defined by formula IV.

R @ 1 represents, for example, a straight or branched alkyl group having from 1 to 5, in particular from 1 to 3, carbon atoms; straight or branched. an alkenyl group or an alkynyl group having from 3 to 5 carbon atoms, or - optionally halogen or a trifluoromethyl substituted benzyl group.

The halogen derivatives of the general formula (IV) are known or can be prepared by customary processes which are generally known in the literature.

The sulphates and sulphonates, as well as other substances required for the production of the active compounds according to the process variant b) according to the process variant b) are generally defined by the formula V.

Solvents preferred for - the preparation of active substances according to - the invention of · the formula I according to process variant a] and b] are as egg dietbylother, ďbutylether, tetrahydrofuran, dioxane, l _r 2-dimethylamino-mesyloxyethane or jejuh mixture with 18-crown-6 ether or dibe nz ο · -18-ro-w n - 6 -e the ry or with di-ethylhylaminamide, Nm <^ t ^ t ^^^^^^ py] rro> li ^ d ^ on or hexaimet ^^^ y Phosphoric acid.

Lithium hydride, sodium hydride, methylmagnetic chloride, methylmagnesium bromide, butyllithium, phenyllithium, sodium, sodium methoxide and the like may be used as basic catalysts. The reaction is preferably carried out at temperatures between -80 to + 80 ° C, preferably between 0 and 6-0 ^° C.

All water-miscible solvents are suitable for the production of metal complexes of the formula II. Suitable solvents are methanol, ethanol, acetone and tetrahydrofuran.

Examples of novel -triazolylglycol ethers are:

2-meťhoox-l- (4'vldm feuo ⁱ ^ y ^ yl- [1,2,4-triazol-l-yl - 3,3-dimtthylbut · an,

2-ethoxy-1- (4‘-chlorophenoxy) -1- [1,2,4-

-triazol-1-yl- | -3,3-dimethylbutane,

2-allyloxy-1- (4-chlorophenoxy) -1- [1,2,4-

-triazol-1-yl-J-3,3-dimethylbutane

2-propargyloxy-1- [4'-chlorophenoxy] -1- [1,2,4-triazol-1-yl] -3,3-dimethylbutane,

2- (4'-chloro ^, benzyloxy) -1- (4'-chlorophenoxy ⁾ -1,14,14,4-triazol-2-ol-1-yl] -1- (4-chlorophenoxy) -1,14,4-diol ^ lb ^ ua ^ n,

2- (4‘-Trifluoromethylbenzoyloxy) -1- (4 '-

- chloro-orphenoxy) -1- [1,2,4-iodo-3,4-dimethyl] -3,3-dimethylbutane,

2- (4'-methoxybenzyl-1'.x.xy) -1- (4'-chlorophenoxy-1- [1,2,4-b] thiazol-4-yl) -3,3-dimethylbutane,

2- (2 ', 4'-Dichloro-4'-ethoxy) -1- (4'-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -33-dimethylbutane,

2- (4'-Bromobenzyloxy) -1- (4'-chloro-4-ynyl) -1- (1,2,4-triazol-M-yl) -3,3-dimethylbutane, 2-benzyloxy- 1- (4'-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -3,3-dimethylbutane, 2-methoxy-1- (4'-bromophenoxy) -1- (1,2,4-triazol-11-yl) -1,3-dimethylbutane, 2-allyloxy-4 (4'-bromophenoxy) -1- [1,2,4-triazole-4-yl] -1-

2-trans-1- (2 х, 4‘-dichlorophenoxy) -1- [1,2,4-

3-Triazol-1-yl] -3,3-methylbutane.

The compounds of formula (I) have two chiral carbon atoms. Thus, they may exist in erythro- and threo-forms. In both cases they occur predominantly in the form of racemates. Erythro and threo forms can be separated (e.g., by column chromatography) and isolated in pure form.

Examples illustrating a process for the preparation of active substances

Example 1 ⁵ cV ~ ^CH V ⁰ vV

29.5 parts (parts by weight) of 1- (4'-chloro-phenoxy) -1- (4-chloro-3-dimethyl-butan-2-ol) are dissolved in 250 To this is added 3.4 parts of sodium hydride (sodium hydroxide) at 10 to 15 ° C under nitrogen, with stirring and ice cooling, and the mixture is stirred at 10 to 15 ° C for 2 hours. The reaction mixture is cooled to 10 DEG C. and 19.7 parts of benzyl bromide are added dropwise at 10 DEG -20 DEG C. After stirring at room temperature for one hour, the resulting suspension is carefully added. The reaction mixture is concentrated in a water pump vacuum, the residue is dissolved in 200 parts of methylene chloride, washed twice with 80 parts of water each, dried over sodium sulphate and concentrated. with 100 parts of petroleum ether, the solvent is decanted, and the residual resin, which is formed The colorless glassy, 2-benzzloxy-1- (4'-chlorophenoxy) -1- (1,2,4-thiazol-1-yl) -3, is a pure substance according to thin-layer chromatogram. 3-Dimethylbutane (active ingredient No. 1) shows the following resonance lines as a mixture of isomers in the 1 H NMR spectrum (220 MHz, C-DC 13):

0.74 and 0.88 (two s, together 9H),

3.12, 3.32, 4.08, 4.13, 4.19 and 4.24 (together 3H),

5.56 (s, 1 H),

5.93, 5.97, 6.03, and 6.07 (q, 2H),

6.2 to 6.5 (m, 7H),

6.96 and 7.07 (d, 1H),

7.31 and 7.43 (d, 1H).

The compounds listed in the following table can be prepared in an analogous manner:

CNo

I O _^CH3 - ^C H

Active substance no.

R1

^{R2 X} H NMR Teplota- / delta (ppm) mixture of isomers mp ° C

2 CHs— 4-C1 resin 270 MHz, CDCl3: 0.87 and 1.07 (two s, together 9H), 3.17 and 3.58 (two s, together 3H), 3.20 and 3.53 (two s, together 1H], 6.3 (d, 1 H), 6.73 (m, 2H). 7.19 (m, -2H); 8.0 (d, 1 H), 8.44 (d, IH). 3 C2H5— 4-C1 resin 220 MHz, CDCh: 0.9 and 1.05 (two s, together 9H), 1.1 (m, 3 H), 3.4 (m, 2H). 6.25 (m, IH); 6.7-7.2 (m, 4H), 7.85 to 7.95 (d, 1H); 8.30 - and 8.42 (d, 1H). 4 CH2 = CH — CH2— 4-C1 resin 270 MHz, CDCl3: 0.88 and 1.07 (two s, together 9H), 3.44 and 3.68 (two m, together 1H), 3.87 and 4.26 - (two m, - together 2H), 5.2 (m, 2H). 5.8 (m, 1H), 6.31 (s, 1 H), 6.86 (m, 2H). 7.2 (m, 2H). 7.98 (d, IH), 8.42 (d, IH).

Active R ¹ substance No,

HC-C — CH2—

R U U-1 NMR / δ (ppm) mixture of isisieres

4-C1 resin 220 MHz, CDCl3:

0.75 and 0.9 (two is, together 9H),

2.2 (d, 1 H),

3.2, 3.35, 3.53 and 3.57 (q, together 2H),

3.97 (s, 1 H),

5.58 (d, 1 H),

6.07 (m, 2H).

6.34 (m, 2H).

7.05 (d, IH);

7.46 (d, IH).

4-C1 resin 270 MHz, CDCl3:

0.91 and 1.07 (two s, together 9H),

3.6 (s), 3.84 (d), 4.36 (d) and 4.73 (q) (together 3H),

6.34 (s, 1 H).

6.86 (q, 2HJ);

7.17 to 7.36 (m, 6H),

8.0 (d, 1 H),

8.36 (d, IH).

4-C1 resin 60 MHz, CDCl3:

1.0 and 1.2 (two s, together 9H),

3.62, 3.7, 3.95, 4.12, 4.4, 4.6 and 4.8 (together 3H),

6.26 and 6.33 (d, 1H),

6.7, 6.84, 7.1 and 7.25 (q, 4H),

7.35 to 7.6 (m, 4H);

7.88, 8.0, 8.2 and 8.36 (q, 2H).

4-C1 resin 220 MHz, CDCl3:

0.82 and 1.02 (two s, 9H),

3.68 (s, 3H);

6.08 and 6.15 (d, 1H),

6.5 to 7.1 (m, 8H),

7.75 (s, 1 H),

8.02 (s, 1 H).

4-C1 resin 220 MHz, CDCl3:

0.76 and 0.91 (two s, together 9H),

3.38, 4.13, 4.19, 4.42 and 4.48 (together 3H),

5.58 and 5.64 (d, 1H),

5.97, 6.0, 6.15 and 6.18 (q, 2H),

6.3-6.6 (m, 5H);

6.98 and 7.08 (d, 1H),

7.28 and 7.45 (d, 1H).

4-C1 resin 2'20 MHz, CDCl3:

0.76 and 0.9 (two s, together 9H),

3.13, 3.33, 4.05, 4.09, 4.14 and 4.19 (together 3H),

5.57 (s, 1 H),

5.95, 5.99, 6.03 and 6.08 (q, 2H)

6.2 to 6.35 (m, 4H);

6.5 to 6.6 (m, 2H),

6.97 and 7.08 (d, 1H),

7.3 and 7.4 (d, 1H).

Active substance no. R1 R2 1 H NMR / δ [ppm] mixture of isomers 11 CHs— [hydrochloride] 2,4-C12 150 to 153 12 CH2 = CH — CH2- [hydrochloride] 4-Br 154 to 157 13 CHj— 4-0r 220 MHz, C-DC13: 0.8'2 and 1.02 [two s, together 9HJ, 3.13, 3,, 2, 3.5 ^ 55 and 3.65 (together 4H), 6.26 to 6.36 (m, 1H) 6.72 to 6.9 [m, 2H] 7.28 to 7.4 [m, 2H] 7.93 and 8.05 [d, 1H], 8.4 and 3.5 3d, 3H]. ·

STEED

Active substance no.

R ²

Ή NMR / a [ppm] mixture of isomers

14 CH3CH2CH2— 4-C1 oil 100 MHz, CDCls [single diastereomer]: 0.62 (t, 3H), 1.0 [s, 9H] 1.4 [m, 2H] 2.8 and 3.2 (m, 2H), 3.3 (d, 1H). 6.2 (d, 1 H), 6.75 (d, 2H). 7.15 (d, 2H). 7.93 [s, 1H] and 8.26 [s, 1H]. 15 Dec CH3CH2CH2CH2— 4-C1 62 to 63 16 CH5 (CH2) 4-- 4-C1 oil 17 CH3 — CH = CH — CH2— 4-C1 oil 270 MHz, -CDCl'3 * J: 0.88 and 1.08 (two s, 9H), 1.7 [two d, 3H], 6.3 [two d, 1H], 6.88 (m, 2H). 7.15 (m, 2H). 7.94 and 8.2 - [d, 1H), 8.38 and 8.52 [d, 1H]. 18 H2C = C — CH2— 1 CH3 4-C1 oil 220 MHz, CDCl3 *): 0.85 and 1.02 (two s, 9H), 1.69 and 1.78 (two s, 3H), 8.03 and 8.5 (two d, 1H each). 19 Dec H3C — C = C — CH2— 4-C1 oil 270 MHz, CDCl 3 [diastereomer j * j: 0.86 (s, 9H), 1.88 (s, 3h), 7.95 and 8.56 [two -s, 1H each]

) only characteristic signals are given

R ^{2 *} H NMR / 5 (ppm) mixture of isomers

4-C1 oil 100 MHz, CDCl3 *):

0.88 and 1.02 (two s, 9H),

7.86 and 8.24 (two d, 1H each).

4-C1 ole) 100 MHz, CDCl3 *]: 0.92 and 1.06 (two s, 9H), 7.96 and 8.32 (two d, 1H each) 4-C1 ole) 220 MHz, CDCl3): 0.86 and 1.02 (two s, 9H), 8.0 and 8.38 (two d, 1H). 4-C1 ole) 220 MHz, CDCl3 *): 0.86 and 1.02 (two s, 9H), 8.0 and 8.38 (two d, 1H each) 4-C1 ole) 220 MHz, CDCl3 *): 0.86 and 1.02 (two s, 9H), 8.02 and 8.4 (two d, 1H).

4-Cl ole) 220 MHz, CDCl3 *):

0.88 and 1.03 (two s, 9H),

8.0 and 8.38 (two d, 1H each).

4-C1 ole)

Cl

4-C1 ol) ^! 270 MHz, CDCl3 *]:

0.84 and 0.98 (two s, 9H),

7.94 and 8.4 (two d, 1H each).

Only characteristic signals are given in 4-C1 (III)

Compounds. according to the invention and their salts and metal complexes are characterized by excellent activity against a broad spectrum of fungi, in particular phytopathogenic fungi, in particular from the class of Ascomycetes and Basidiomycetes. These compounds are in part systemically active and can be used as foliar fungicides and soil fungicides, but in particular also as mordants.

Of particular interest are fungicidal compounds for the control of a variety of fungi on various crop plants or their seeds.

Crops in this context include, in particular, wheat, rye, barley, oats, rice, maize, bavaria, soya, coffee, sugarcane, fruit and ornamental trees and horticultural plants, as well as vegetables such as cucumbers, beans and pumpkin plants.

The novel compounds are particularly suitable for combating the following plant diseases:

powdery mildew (Erysiphe graminis) on -cotton, beetle (Erysiphe c.ichoriacearum) on pumpkin plants, apple powdery mildew (Podosphaera - leucotricha) on apple trees, powdery mildew (Uncinula necator) on grapevine, powdery mildew (Erysiphe polygoni) powdery mildew of peach (Sphaerotheca pannosa) on roses, Puccinia species on -coffee, Hemileia vastatrix on coffee plants, bean rust (Uromyces phaseoli) on beans,

Ustilago-nuda -to barley,

Ustilaggers and Tilletia tritici on wheat.

The novel active compounds are furthermore suitable for application in the protection of materials, in particular in the protection of wood and wood products against decomposition caused by fungi of the Basidiomycetes class. the following fungi may be mentioned individually: Conioiphora - puteana, Merulius lacr ymans, Porta rnonticola, Lenzites trabea, Lenzites abietina, - Trametes versicolor, Armillaria mellea, Sterum purpureum, Fomes annosus.

The substances according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules. The use forms depend entirely on the intended use. In any case, they are intended to ensure a fine and even distribution of the active ingredient. The compositions are prepared in a manner known per se, for example by mixing the active compound with solvents and / or carrier substances, optionally using emulsifiers and dispersants, and other organic solvents can also be used as co-solvents when water is used as a diluent. basically suitable auxiliaries are: solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g. ethanol amine, dimethylformamide) ) and water; carriers such as natural stone meal (for example kaolins, clays, talc, chalk) and synthetic stone meal for example highly disperse silicic acid and silicates; emulsifiers, such as non-ionic and anionic emulsifiers, for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates and dispersants, such as lignin, sulfite waste liquors and methylcellulose.

The fungicidal compositions generally comprise between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90% by weight of active ingredient.

The compositions or preparations prepared therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are used in a known manner, for example by dusting, fogging, spraying, spreading, pickling or potting.

Depending on the type of effect desired, the application rate is between 0.01 and 3 or more, preferably between 0.01 and 1 kg of active substance per ha.

The active compounds can also be mixed together with other active compounds, for example herbicides, insecticides, growth regulators and fungicides, or also with fertilizers and applied in the form of a mixture. In many cases, an increase in the spectrum of fungicidal effect is also obtained when mixed with the fungicides. In many of these fungicidal mixtures, synergistic effects also occur, i.e. the fungicidal activity of the combined product is greater than the sum of the activities of the individual components.

The following list of fungicides, which may be combined with the active ingredients, is intended to illustrate the possibilities of the combinations described above, but in no way limits the scope of these possibilities.

Fungicides that can be combined with the active ingredients are, for example:

Dith-ethylthiocarbamate and derivatives of them, such as ferric dimethyldithiocarbamate, ·, CimethylCith'ok.arbamát zinc ethylene-bis-dithiocarbamate, manganese ethylenCiamin-bis-t Cithiokarbamá ^L manganese zlnečnatý, ethylene-dithiocarbamate b's - zinc tetramethylthiur amCisulfiCy _1, zinc ammoniacal complex of zinc-, Ν-ethylene-bis-dithiocarbamate and N, N'-piDl-4'-ethylene-bis- (thiocarbamoyl) disulfide,

Zinc N, N‘-propylene-bis-dithiocarbamate, ammoniacal complex of N, N‘-propylene-bis-

zinc di-thiocarbamate; and N, N‘-polypropylene-bis- (thiocoxocarbamoyl) disulfide.

Nitro-derivatives such as di-triphenylmethyl (phenyl) crotonate,

S-sec-but-1-4,6-thiophenophenyl-3,3-dimethyl acrylate,

2-isopropylphenylisopropyl-4-carbonate.

Heterocyclic compounds such as N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide,

2,4-ε-β-ω-6- [o-chloro-kno] -s-triazine, 0,0diethylphthiimidophosphonothioate,

5-amino-1- (bis- [dimethylamino-ino] phosph (nyl) -

-3-phenyl-1,2,4-triazole,

5-ethoιxy-У-LR: c'hloomathy ^ lI2I4-th 2,3čdikyan ^{thiadiazol-l,} 4-d (thiaanthrachmon 2-yo-th 13Mi.thio- [4,5-b] quinoxaline, methyl 1- (Butyloxycarbamoyl) -2-benz- (billionaisolcarbamic acid),

2 - ^^ 1 ^^ l ^^ and ^^] ^ J ^ d ^] ^ - ^^ Bo: ylamino ^s.-Nob]: ^ i ^ -m-imidazo l 2črhodanmethyΓthobenzthiazol,

4- (2-Chloro-phenylhydrazono) -3-methyl-5-

isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline, and optionally its copper salt, 2,3 ^; -dihydi ^ o ^^^ 5-kai ^ boixaniik ^ (^ '6 ^ - ^. me1: hyl-1,4-хх1111иии-4,4-С ^ ^),

2,3-dihydro-5-carboxanilido-6-methyl-1,4-ooxathiin,

2- (1α-2-β-benzimidazole, piperazin-1,4-d (γ-bis- (1- [2,2,2-trichloroethyl]) - formamide),

2- (thiazol-4-yl)

5-Butyl-2-dimethylamino-4-hydroxy-6-

-methylpyrimidine, bis- (p-chlorophenyl) -4-pyridine-methanol,

1,2-bis- (S-ethoxycarbonyl-4-nitro) benzene,

1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene, and various fungicides, such as dodecylguamdin acetate,

3- (3- [3,5-dimethoxy-γ-oxy-cyclohexyl] -2-

-hydroxyethyl] glutarimide, hexachlorobenzene, N-dichlorofluoromethylthio-N ‘, N‘ -dimethyl-N-phenylamide sulfuric acid,

2,5-dimethylfuran-3-carboxanilide, cyclohexylam ^: d 2,5 ^^ 0 ^ 1 ^^^ 3-

-carboxylic acids,

2-methylbenzyl ^{and ZAMI;} d, Z-iodo-benzanilide,

1- (3,4-d 'chloranilino) -1-formylamino-

2,6-dimethyl-N-tridecylmorpholine or its salts,

2.6- d (methyl-N-cycl dodecyl ^ o ^ ^ m ^ i ^ violin or its salts ^1,

N- [3- (p-tert-butylphenyl) -Z-tert-propyl] cis-2,6-dimethylmorpholine,

N- [3- (p-tert-butylphenyl) -2-methylpropyl] -3,5-dimethylpiperidine,

N- [3- [p-tert-butylhenyl] -2- [beta] -R-opyl] piperidine,.

methyl N-22,6-2-methylenyl) -N- (2-furoyl) alaninate, methyl 1-N- (2,6-dimethylphenyl) -N- (2-methoxy-acetyl) alaninate,

N- [2,6-dimethylphenyl) -N- [2-oxotetrhydrofuran-3-yl] chloroacetamide,

An alkyl-2- N-ethyl-m ^ and ⁿ ^ o ^ ^{ikarbonyl-2-m} eithoximinoacetamid,

5-nitroisophthalic acid, di-isopropyl ester,

3- [3,5-Dichloro-phenyl] -5-methyl-5-ethenyl;

-2,4-oxazohindine · on,

3- (3,5-Dichloro-phenyl) -2,4-d: oxo-1- [N-isoprop-yl] imidazolidinecarboxamide, N- (3 ', 5'-dichlorophenyl) im'd 1,2 -dimethylcyclopropanedioic acid;

· N‘-hydroxy-N-cyclohexyldiazenium oxide aluminum salt, cyclohexyl · aodide of N-methoxy-2,5-dimethylfuran-3-carboxylic acid.

The following examples illustrate the fungid effect of the novel active ingredients.

Compounds described in DOS 2,063,857 corresponding to formula A ci were used as comparators

0CH2CH = CH _from

AND

This compound will hereinafter be referred to as Compound A for simplicity. Example 2

The leaves grew ^: n "Juibilar" pests growing in pots were sprayed with an aqueous emulsion consisting of 80% by weight of active ingredient and 20% by weight of emulsifier, and after spraying, the powdery mildew was dusted with powdery mildew (Erys (phe gram) The test plants are then placed in a greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative air humidity.

The test results are shown in the following table:

TABLE of infestation of leaves after spraying x.% Suspensions of the active substance active substance

C. x = 0.006 0.012 0,025 2, 0 0 0 4 0 0 0 5. 0 0 0 6 ' 1 0 0 AND 4 3 3 inspection (untreated) 5

= no attack, graduation up to 5, which is the total attack.

Example 3

In a further test, as described in the above example, the leaves of barley plants in pots of the "Frybecks Union" type are treated with the active ingredients and then dusted with powdery mildew (Erysiphe grimsims var. Hordei).

The test results are shown in the following table:

TABLE

active substance no. attack x = 0.006 2 0 4 0 5 0 6 0 AND 2 inspection (untreated) 5

sprayed by spraying x% active substance suspensions

0,0120,025

Example 4

L ^; The hundred plants of 'Caribo' wheat growing in pots are dusted with rust spores (Puccinia recondha). The flower pots were then placed in a high humidity (90-95%) chamber at 20-2.2 ° C for 24 hours. During this time the spores germinate and the germs penetrate the leaf tissue. The infected plants are then sprayed with aqueous suspensions containing 80% by weight of the active ingredient and 20% _by weight _of lignin sulphonate until dry. After the spray layer has dried, the test plants are placed in a greenhouse at room temperature. temperatures between 20- and 22 ^? And 65 to 75% relative humidity. After 8 days, the degree of rust development was found to be 1 hundred.

The test results are shown in the following table:

active substance no.

infestation of leaves after spraying x% active substance suspensions

X = 0.006 0.012 2 0 0 4 0 0i 6 1 1 AND 5 5 inspection (untreated) 5

• 0.025

IS

Example 1 a d 5 ....

100 g of barley seed of Asse type are carefully n-immersed in glass bottles for about 5 minutes using 3ΌΌ mg (= 0.3% by weight) of the gauge in the table. Then, 8 grains are placed in a pot and the grains are covered with soil. powdery mildew Erysiphe graminte var. hordei. The test is then grown jny · - -skleníku exposed at temperatures between 20 and 22 ° C. 6 ^l at 5-70% relative humidity. · After a further 10 days the degree of mildew development on the leaves is determined.

Test results - are shown in the following table:

active substance no. . . . % active substance in meoidle The degree of powdery mildew infestation on the leaves of 10-day PC artificial infection 2 10 , 0 5 10 0 6 10 0 control (heoed 1  '- 5

Example 6 parts by weight of the compound. are mixed with 10 parts by weight of N-methyl-.alpha.-pyrroE.donu give a solution which is suitable for use as a • ^d m its minimum droplets.

Example 7 parts by weight of compound 2 are dissolved in a simulation consisting of 80 parts by weight of xylene, 10 parts by weight of an adduct of 8 to 10 moles of ethylene oxide. - with 1 mole of - N-monoethanolamide oleic acid, 5 parts by weight of dodecylbenzenesulfonic acid calcium salt and 5 parts by weight of an admission product - 40 moles of ethylene oxide with 1 mole of ricmole oil. Then, by finely distributing this solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient. .

EXAMPLE 8 parts by weight of Compound 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide with 1 mol of isooctylHenohi, and 10 parts by weight. 40% ethylene oxide with 1 mole of castor idea. By pouring the solution into 100,000 parts by weight of water gives an aqueous dispersion which contains by weight 0.02 / ₀ of the active ingredient.

EXAMPLE 1- 20 parts by weight of the compound are dissolved in a mixture consisting of 25 parts by weight of cyclobexanol, 65 parts by weight of a mineral oil fraction, boiling point 210-280 ° C, and 10 parts by weight of an addition product. 40 moles of ethylene oxide with 1 mole of castor oil. Pouring and finely distributing this solution in 100,000 parts by weight of water gives an aqueous dispersion. which contains 0.02% by weight of the active substance. .

For example, parts by weight of active ingredient 2 are mixed with 3 parts by weight of the di-isobutyl sodium salt of α-α-sulphate. The fatty acids, 17 parts by weight of the sodium salt of P-sulphonic acid from sulphite waste liquors and 60 parts by weight of powdery silica gel, and - after thorough mixing, the mixture is ground by means of a milling mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

EXAMPLE 11 Parts by weight of Compound 3 are mixed intimately with 97 parts by weight of finely dispersed kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

EXAMPLE 1 a d 1 2 parts by weight of compound 4 are mixed intimately with the mixture consisting of 92 parts by weight of a powder-yellow silica gel and 8 parts by weight of paraffin-oil sprayed onto the surface of the sibecagel. In this way, the active ingredient preparation with good adhesion is obtained.

Example 13

The parts by weight of the active compound 1 are intimately mixed with 10 parts by weight of the sodium salt of the condensation product of phenolsulphonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which contains 0.04% by weight of the active ingredient.

Example 14 parts by weight of active ingredient 2 are intimately mixed with 2 parts by weight of dodecylbenzenesulfonic acid calcium salt, 8 parts by weight of polyglycol ether of fatty alcohol, 2 parts by weight of sodium salt of phenolsulfonic acid, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

Example 15

To obtain an oily wood preservative containing 0.5% by weight of 2-methoxy-1- (4'-chlorophenoxy) -1- [1,2,4-triazol-1-yl] -3,3'-dimethylbutane (active substance

2) 0.5 parts of the active ingredient are mixed with 15 parts of a medium oil alkyd resin (20% solid resin). 45 parts of the aromatic-containing benzoic fraction are then added, and the mixture is then filtered to remove impurities and then topped up with 100 parts of the aliphatic hydrocarbon-containing gasoline fraction.

In an analogous manner, 1 and 2% oily wood preservatives containing 2 are prepared.

Example 16

To determine fungicidal activity against Cen phora puteana and Trametes versicolor fungi, 50 x 25 x 15 mm pine wood top blocks are coated with wood preservatives containing 0.5, 1 and 2% of active ingredient each 200 g / m ² of wood surface. After four weeks of storage, the treated logs together with the untreated logs are placed in glass dishes containing the test mushroom Coniophora puteana or Traimeteis versicolor orally on nutrient agar. The trays are then kept in an air-conditioned chamber at 22 ° C and 70% relative humidity. After three months of the experiment, the blocks are freed from the adherent fungal mycelium and dried. The degree of wood failure is then determined.

The test results are shown in the following table:

active substance no.

the degree of fungal infestation after three months of the experiment

...% of active substance in the preparation

What about phora puteana

Trametes versicolor

2 0.5 1 1 1 1 1 2 1 1 4 0.5 1 1 1 1 1 2 1 1 pentachlorophenol 1 3a 3a (known active substance) 2 2b / 3a 2b control (alkyd only) - 3a / 4b 3b

resin + solvent, no active substance)

The assessment of timber failure was carried out according to the following scale:

pattern intact

2A sample is infested here and there

2b the sample is not infested in its entirety

3The sample is strongly attacked here and there

3b the sample is strongly attacked in its entirety

4a sample of ITU and there completely damaged (destroyed)

4b the sample is completely destroyed in its entirety

Claims (1)

OBJECT OF THE INVENTION A fungicidal composition comprising a solid or liquid carrier and as active ingredient at least one triazolyl glycol ether of the general formula: R 1 represents an alkyl group of up to 5 carbon atoms, an alkenyl group of 3 to 5 carbon atoms, an alkynyl group of 3 to 5 carbon atoms, or; a benzyl group optionally substituted by a halogen or a trifluoromethyl group, R ² represents a halogen atom and n represents the number · 1 or; 2,. or a metal salt or complex thereof.